Dyestuffs of the anthraquinone series



"carboxylic acid chloride], chloro-anthraquinone-ZJ-(N) -1'.2' o (N) benatented June 10, 1941 f UNITED STATES PATENT OFFICE DYESTUFFS OF THE ANTHRAQUINONE Fritz Baumann and Heinz-Werner Schwechten, Leverkusen-I. G. Werk, Germany, assignors to General Aniline & Film tion of Delaware Corporation, a corpora No Drawing. Application March s, 1938, Serial 4 Claims.

- acridones which contain carboxylic acid groups in form of their corresponding acid halides. Preferably those a-arylamino-anthraquinone-2.1-

, (N) -1'.2'-(N) -acridones are used as starting materials which have the carboxylic acid group in the aryl nucleus and which correspond to the .general formula wherein Aqa stands for an anthraquinone-benzacrldone or anthraquinoneanaphthacridone and 'theGreek letter a means thatfthe nitrogen atom is attached in alpha-position to the anthraquinone nucleus of the anthraquinone-acridone ring system Compounds oi'this kind are, for instance, anthraquinone-2.l-(N) -1'.2 (N) -.benzene-acridone--[anilido-p-carboxylic acid chloride], anthraquinone-2.1-.(N) -1'.2.,'-(N) -benzeneacridone i- [anilido-m-ca'rboxylic .acid chlorine], 4-chloro resp. 5'- -chloro-anthraquinone 2.1- (N) -l'.2'-(N) -benzene-acridone-4 r- [anilido-p- 4'-chloro resp.5'-

z ene-acridone-i-[anilido-m-carboxylic acid chloride], 3 .5'.- dichloro anthraquinone 2..1 :(N) 1'.2' N)'-benzene acridone-4-[anilidop carboxylic acid chloride], anthraquinone2.1-(N),- 1C2 (N) 7 benzene-acridone-5-[anilido-p-carboxylic acid chloride], 3' .5'-dichloro-anthraqui none-2.1-(N)-1'.2'-(N) benzene-acridone-o-fi Ianilido-p-carboxylic acid chloride], 5'-chloroanthraquinone 2.1 (N) 1'.2'-(N)-benzeneacridone-8-[anilido-m-carboxylic acid chloride], and anthraquinone-2.1-(N)-1'.2'-(N) -naph thacridone-5-[anilido-p-carboxylic acid chloride].

The u-aryl amino anthraquinone 2.1-(N) 1'.2-(N)-acridone-carboxylic acids used as starting materials can be obtained, for example, by reacting and a-amino-ranthraquinone-2.1- (N) -1'.2'-(N) -acrid or re upon a ha1ogen-arylcarboxylic acid ester, as, for instance, a p-, m-, or o-halogen benzoic acid methylor ethyl-ester or a halogen-naphthoic acid ester. In the reaction product thus obtained the acid ester group is saponified in the usual way, and the carboxylic acid so formed is treat d wit ge s be ng a- In Germany March 17, 1937 chloride.

pable of forming acid halides such as thionyl- Another type of starting materials is obtained by causing anthraquinone-1.4-dihalogen-2-carboxylic acids to react with 1 .mol of an aminobenzoic acid ester, whereby an anthraquinoneacridone ring system is formed, and then replacing the halogen atom in ii-position by an arylamino. radical. The ester obtained is saponified to the, carboxylic acid and the carboxylic acid group is transformed into the acid chloride group. By this way'also dicarboxylicacids can be obtained either by causing lA-dihalogen-anthraquinone-2-carboxylio acids to react at first with at least 2 mols of an amino-benzoic. acid ester or successively with 1 mol of two different amino-benzoic acid esters.

group an OH-, SH-onNI-lR-group (B. being hydrogenyalkyl, or aryl),- a ring formation'takes place-and an oxazol'e, thiazole or imidazole ring system results.

-The reaction of the carboxylic acid halides with the amines is carried. out at an elevatedtemperature and in the amine itself as solvent or in the presence of an'in'd'ifferent solvent such" as'odichloro-benzene, trichloro benzene, nitro-benzene, ch'JorO naphthaIene, or ethyl-carbazole.

In case an amino-anthraquinone is used bearing in o-position a group being capable offorming a ring with the amino group (an OI-I-, SH- or NHR-group) the reaction temperature reached, for instance; by working in nitrobenzene is not sufiicient'i'n order to effect the splitting off of water and ring formation. In these cases an additional heating of the first formed reaction product in a high boiling solvent as, for instance,

ethyl-carbazole is necessary.

The products thus obtained are vat dyestuffs which if prepared from a-arylamino-anthraquinone-2.1 (N) -1.2-(N) -acridone carboxylic acids having the aryl radical in i-position dye cotton yellowish green shades, but if prepared from the same acids having the aryl radical in 5- or 8-position dye cotton violet-brown to blackbrown shades. The new dyestuifs show-excellent Example 1 11 parts of a-amino-anthraquinone are heated in 800 parts of nitrobenzene up to 120 0.; at this temperature 24 parts of 3'.5'-dichloro-anthraquinone-2.1-(N) -1.2'- (N) benzene-acridone -4- [anilido-p-carboxylic acid chloride] are added to the solution and then stirred at 130 0., until the evolution of hydrochloric acid has ceased. The dyestufi is filtered with suction at 90 C., washed with nitrobenzene and then dried. The green dye-powder shows a Bordeaux-red color of the vat and dyes cotton green shades.

By using 1-amino-5-benzoyl-amino-anthraquinone instead of a-amino-anthraquinone a product is obtained which dyes cotton yellowish to olive green; 4-amino-1.Q-anthrapyrimidine also yields an olive green .dyestuff. n the other hand, when reacting the acid chloride with 4- amino chloro-anthraquinone-2.1-(N) -1'..2-'- (N) -benzene-acridone, a dyestuff is obtained which dyes vegetable fiber greenish blue.

The carboxylic acid chloride used in the reaction is obtained, for example, by the condensation of 4-amino-3'-5'-dichloro-anthraquinone- 2.1-(N)-1-2'-(N) -benzene acridone with pbromo-benzoic acid methyl-ester in a solution of nitrobenzene and in the presence of potassium acetate and copper; the ester obtained crystallizing in blue to black needles is saponified in an alkaline medium and the carboxylic acid is transformed into the chloride by means of thionyl-chloride in trichloro-benzene at a temperatureof 90- 95" C.

Example 2 p 5 parts of 3-5'-dichloro-anthraquinone-2.l- (N) 1.2'-(N) benzene-acridone-i-[anilido-mcarboxylic acid chloride] obtained'according to Example 1 are slowly heated to boiling with 2.5 parts of a-arnino-anthraquinone in 160 parts of anhydrous trichloro-benzene. When the carboxylic acid. chloride is transformed the diflicultly soluble dyestufi' is filtered with suction at 120 C., washed with pyridine and dried. The substance crystallizing in green needles dyes cotton from the vat green shades.

Example 3 They dissolve in concene They are difiicultly 26 parts of 5'-chloro-anthraquinone-2.1-(N)- C. In this way the dyestuff of the following 1-0 constitution A (If 1 i0 I? Y NHO-o Y is obtained in form of beautiful green crystals, which dissolve in sulfuric acid with yellow-brown color and yield on cotton from a red-brown vat on oxidizing yellowish green shades. By using 1- amino-2-hydroxy-anthraquinone instead of 2- amino-3-hydroxy-anthraquinone the isomeric 2- l-oxazole is obtained which dyes cotton strong greenish olive shades. By using a higher boiling solvent in the reaction instead of nitrobenzene, the pure oxazole is obtained immediately.

Example 4 A mixture of 13 parts of 5chloroanthraquinone 2.1 (N) 1.2' (N) -benzene-acridone-4- [anilido-p-carboxylic acid chloride] and '7 parts of 2- amino-3-mercapto-anthraquinone is added to 400 parts of u-chloro-naphthaleneat 120-130 C., whereupon I the reaction mixture is slowly heated to 260 C. At the boiling temperature green needles separate from the green solution. The solution is heated to boiling .for about 30 minutes and the green dyestuff is filtered off at C. After drying the dyestuff is obtained in form of a green powder which, after being crystallized fromquinoline, dyes cotton from the vat yellow-green shades. 1

When reacting 4 chloro anthraquinone-2.l- (N) 1.2' (N) -benzene-acridone-4-[anilido-pcarboxylic acid chloride] upon 2-amino-3-mer- 'capto-anthraquinone a thiazole is obtained which dyes cotton bluish green shades.

The thiazoles obtainable from l-mercapto-zamino-anthraquinone represent olive green dyestuffs. 1

Example By causing to react 26 parts of 5'-chloro-anthraquinone 2.1 (N) 1'.2-( N) benzene-acridone-4- [anilido-p-carboxylic acid chloridel upon 18 parts of 1anilido-2-amino-anthraquinone in 40 parts of a-chloro-naphthalene at a temperature of 260 C. for one hour a dyestuff of the following constitution is obtained which is filtered with suction at room temperature. It can be recrystallized from nitrobenzene and dyes cotton green shades from the vat.

Ewample 6 2'7 parts of 3'.5dichloro-anthraquinone-2.1- (N) 1'.2' (N) benzene-acridone-5-[anilido-pearboxylic acid chloride] and 12 parts of l-amino- Z-hydroxy-anthraquinone are heated to boiling for some hours in 800 parts of nitrobenzene. The dyestufl. thus obtained is filtered with suction; washed with nitrobenzene and then dried.

The dyestuff is subsequently heated to boiling in ethyl-carbazole and then filtered with suction at 100 C. after being diluted with pyridine. A

dyestuff of the following constitution is obtained in form of red-brown needles. The dyestufi is soluble in concentrated sulfuric acid with yellow-brown color. It dyes vegetable fiber from bluish red vat black-brown shades.

By using anthraquinone 2.1 (N) 1'.2'-(N) benzene-acridone-E-[anilido p carboxylic acid chloride] resp.anthraquinone-2.1- (N) -1'.2'-(N) naphth acridone 5 [anllido-p-carboxylic acid chloride] instead of 3'.5 dichloro anthraquinone 2.1 (N) 1'.2 (N) benzene-acridone-5- [anilido-p-carboxylic acid chloride], dyestuffs are obtained which yield on vegetable fiber shades similar to those obtainable by the above dyestufi.

By using 1 hydroxy Z-amino-anthraquinone resp.1amino-Z-mercaptoanthraquinone instead of 1-amino-Z-hydroxyanthraquinone, the corresponding oxazoles or thiazoles are obtained which show similar dye-properties.

By using as starting material 2-amino-3-hydroxy 'anthra'quinone and" 3' .5'-dichloro-anthraquinone-ll (N) '-'1" .2' (N benzehe. acridone-5- [anilido-p-carboxylic acid chloride] products are obtained yielding greyish colors.

Example 7 55 parts of 8.5'dichloro-anthraquinone-2.1- (N) 1'.2' (N) benzene-acridone-5-[anilido-pcarboxylic acid chloride] and 25.5 parts of l-mercapto-2-amino-anthraquinone are slowly heated in 1500 parts of chloro-naphthalene to the boiling point of chloro-naphthalene and stirred for about one hour at this temperature. The reaction product is isolated at room temperature in the usual manner.

When the reaction product is heated in ethylcarbazole and precipitated with pyridine the dyestufl' is obtained in form of black-brown needles. It dyes cotton from red-violet vat nigger-brown shades. The solution in sulfuric acid is yellowbrown. 7

Example 8 5 parts of 5'-ch1oroanthraquinone-2.1-(N 1'.2'- (N) benzene-acridone 4 [anilido-p-carboxylic acid chloride] and 5 parts of dehydrothiotoluidine are heated to boiling in 100 parts of nitrobenzene for about /1 hour, whereby the corresponding acylamine crystalliz'ing in long fine needles is obtained, hydrogen chloride being split off. The product can be worked up in the usual manner; it is soluble in sulfuric acid with yellow color and precipitates in clear green flakes after diluting the sulfuric acid solution with water.

The product can be used as suitable formation.

We claim:

1. The compounds of the formula wherein Aqa stands for an anthraquinone-acridone selected from the group consisting of the benzand nalphth-acridones, the Greek letter or means that the nitrogen atom is attached in a1- pha-position to the anthraquinone nucleus of the anthraquinone-acridone, A stands for an anthraquinone radical and X stands for a. linking radical of the class consisting of O, S, and

R1 standing for a member selected from the group consisting of hydrogen, alkyl and phenyl.

2. The compounds of the formula XIA R1 standing for a member selected from the pigment after 3. The compound of the following formula:

group consisting of hydrogen, alkyl, and phenyl.

FRITZ BAUMANN.

HEINZ-WERNER SCHWECHTEN. 

